Sulfate radical-based water treatment in presence of chloride: formation of chlorate, inter-conversion of sulfate radicals into hydroxyl radicals and influence of bicarbonate.

Sulfate radical (SO4(-)) based oxidation is discussed as a potential water treatment option and is already used in ground water remediation. However, the complex SO4(-) chemistry in various matrices is poorly understood. In that regard, the fast reaction of SO4(-) with Cl(-) is of high importance since Cl(-) belongs to the main constituents in aqueous environments. This reaction yields chlorine atoms (Cl) as primary products. Cl initiate a cascade of subsequent reactions with a pH dependent product pattern. At low pH (<5) formation of chlorine derived oxidation products such as chlorate (ClO3(-)) is favoured. This is undesired because ClO3(-) may reveal adverse effects on the environment and human health. At pH > 5 Cl mainly react with water yielding hydroxyl radicals. Thus, at moderate Cl(-) concentrations (mM range) the SO4(-)-based process may be converted into a conventional (hydroxyl radical -based) advanced oxidation process. The conversion of SO4(-) into OH, however, is interrupted in presence of bicarbonate by scavenging of Cl.